CN101086073A - Technology for direct electrolysis for preparing TiO2 under vacuum condition - Google Patents
Technology for direct electrolysis for preparing TiO2 under vacuum condition Download PDFInfo
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- CN101086073A CN101086073A CNA2006100121800A CN200610012180A CN101086073A CN 101086073 A CN101086073 A CN 101086073A CN A2006100121800 A CNA2006100121800 A CN A2006100121800A CN 200610012180 A CN200610012180 A CN 200610012180A CN 101086073 A CN101086073 A CN 101086073A
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- electrolysis
- tio
- tio2
- titanium sponge
- negative electrode
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Abstract
The invention relates to a method for preparing titanium sponge. It comprises following steps: heating distilled water to 95 Deg. C, adding polyvinyl alcohol, thermal insulating and stirring to gruel mixture, then adding TiO2 powder; the average particle size of TiO2 powder is 0.35 um, purity is above 98%, the weight of polyvinyl alcohol is 5- 8% of that of TiO2, distilled water is 8- 10% of that of TiO2; mixing evenly and pressing under 5- 15 Mpa pressure for shaping, and getting TiO2 cathode, said TiO2 cathode is naturally dried for 24- 48 hours and calcinated at 800- 1200 Deg .C for 5- 10 hours. Taking TiO2 cathode as cathode, high- purity graphite as anode, electrolyzing with calcium chloride fused salt in specific vaccum electrolysis furnace equipped with titanium electrolyser, the electrolysis temperature is 800- 1100 Deg. C, time is for 5- 12 hours, voltage is 2.8- 3.3, cooling electrolyzed product to room temeprature, collecting spongy substance on the surface of electrode and washing with 1% HCl, getting titanium sponge, with purity being above 99.5%.
Description
Technical field
The present invention relates to the novel preparation technology of titanium sponge, mainly is to adopt vacuum condition in CaCl
2Direct electrolysis TiO in the molten salt system
2The preparation titanium sponge.
Background technology
Fused salt electrolysis TiO
2The preparation titanium sponge is one of focus of studying among the titanium preparation method in the world at present, this method because possess the production process simplification, production cost is low, quality product is high, advantages of environment protection is considered to the most promising, the most noticeable, most possibly replaces the titanium sponge novel preparation method of Kroll method.At present, adopt fused salt electrolysis TiO
2The research of preparation titanium sponge just has been in the starting stage, is considered to one of global problem in the titanium sponge preparation field.
Do not see as yet on the domestic patent documentation about direct electrolysis TiO
2The report of preparation titanium sponge.Though on some other non-patent literature relevant for direct electrolysis TiO
2The report of preparation titanium sponge, but all relevant reports are all carried out direct electrolysis TiO under vacuum condition under protective atmosphere
2The preparation titanium sponge is not seen relevant report at present as yet.
Summary of the invention
The present invention overcome the deficiencies in the prior art provide a kind of under vacuum condition at CaCl
2Direct electrolysis TiO in the molten salt system
2The new technology of preparation titanium sponge.
The present invention is 0.35 μ m with mean particle size, the TiO of purity＞98%
2Powder and weight ratio are TiO
2After 5～8% polyvinyl alcohol of powder and 8～10% distilled water mix and stir, under 5～15MPa, after making type, mould inner pressure makes electrode, described electricity level at room temperature behind seasoning 24～48h, at 800～1200 ℃ of following sintering 5～10h, makes TiO
2Negative electrode is anode, described TiO with the high purity graphite
2Negative electrode is made negative electrode, in special vacuum electrolytic furnace in the titanium metal electrolyzer in 10
-4～10
1Carry out electrolysis in the calcium chloride fused salt under the Pa, electrolysis temperature is 800～1100 ℃, electrolysis time is that 5～12h, electrolysis voltage are 2.8～3.3V, after electrolysis finishes, electrolysate is cooled to room temperature, collector electrode surface spongy material and with the 1%HCl washing, prepared electrolysate is a titanium sponge, purity reaches more than 99.5%, reaches national titanium sponge primary standard.
An alternative embodiment of the invention is described TiO
2The negative electrode diameter highly is the cylindric of 50～100mm more than or equal to Φ 50mm.
TiO that an alternative embodiment of the invention is used
2Negative electrode is the length of side 100～180mm, highly is the square tabular of 5～10mm.
Processing condition of the present invention are:
TiO
2Powder: mean particle size 0.35 μ m, purity＞98%, crystal formation are anatase titanium dioxide;
Polyvinyl alcohol: reagent, analytical pure;
Water: reagent, analytical pure;
TiO
2Powder: polyvinyl alcohol: water (weight ratio)=100: 5～8: 8～10;
TiO
2Powder, polyvinyl alcohol, water blended temperature: 90～100 ℃;
Forming pressure: 5～15Mpa;
TiO
2The electrode seasoning time: 24～48h;
TiO
2Electrode sintering temperature: 800～1200 ℃;
Sintering time: 5～10h;
CaCl
2Fused salt: reagent, analytical pure;
High purity graphite: purity＞96%;
Electrolysis pressure: 10
-4～10
1Pa;
Electrolysis temperature: 800～1100 ℃;
Electrolysis time: 5～12h;
Electrolysis voltage: 2.8～3.3V;
Electrolysate washing reagent: 1%HCl solution;
Electrolytic process temperature-rise period: be evacuated to 10
1Be warming up to 500 ℃ and be incubated 2h behind the Pa, slough CaCl
2Moisture in the fused salt is warming up to electrolysis temperature and begins electrolysis.
Some explanation to technical process of the present invention:
1, TiO
2The preparation of electrode is one of electrolytic process key of success technology, sintering temperature of the present invention between 800～1200 ℃, prepared TiO
2The crystal configuration of electrode changes rutile-type into by anatase titanium dioxide and the intergranular space rate is 40～60%.
2, the electrolytic process heating curve is another key problem in technology of electrolysis success or failure, and heating curve of the present invention is: in vacuum tightness 10
1Just begin under the Pa to heat up, be warming up to 500 ℃ and be incubated 2h, be warming up to electrolysis temperature again.
The present invention has following advantage:
1. electrolysis TiO under vacuum condition
2The preparation titanium sponge is not seen relevant report at present all documents.
2. with direct electrolysis TiO under protective atmosphere
2The preparation titanium sponge is compared electrolysis TiO under vacuum condition
2In the preparation titanium sponge technology, on the one hand with CaCl
2The dehydration of molten salt system and electrolysis temperature-rise period are united, and owing to the negative pressure atmosphere, make that the preelectrolysis step is omitted, thereby have further simplified technical process on the other hand.The quality that is expected greatly to have reduced the production cost of titanium and improves product.
3. adopt electrolytic process to prepare the simple substance titanium, the gas of separating out at anode is CO and CO
2Mixture, be easy to control, pollution-free, overcome the by product Cl in the traditional technology process
2And condition such as production process mesohigh is to the negative impact of environment.
Embodiment
Be described in further detail below in conjunction with embodiment.
Embodiment 1:
With TiO
2Powder and weight ratio are TiO
2After 8% polyvinyl alcohol (PVA) of powder and 10% distilled water mix and stirs, make the electrode that diameter is 50mm, high 6mm after the mould inner pressure of Φ 50 is made type under 12MPa.After at room temperature doing 48h naturally,, make TiO at 800 ℃ of following sintering 8h
2Negative electrode.With the high purity graphite is anode, TiO
2Electrode is made negative electrode, in special vacuum electrolytic furnace in the titanium metal electrolyzer in 10
-1Carry out electrolysis in the calcium chloride fused salt under the Pa, electrolysis temperature is 900 ℃, and electrolysis time is that 6h, electrolysis voltage are 2.8V.After electrolysis finishes, electrolysate is cooled to room temperature, collector electrode surface spongy material also washs with 1%HCl.Prepared electrolysate is spongy, and purity is 99.663%, reaches national titanium sponge primary standard.
Embodiment 2:
With mean particle size is 0.35 μ m, the TiO of purity＞98%
2Powder and weight ratio are TiO
2After 7% polyvinyl alcohol (PVA) of powder and 9% distilled water mix and stirs, suppress to such an extent that diameter is the electrode of 50mm, high 8mm after under 14MPa, making type in the mould of Φ 50.After at room temperature doing 36h naturally,, make TiO at 1000 ℃ of following sintering 6h
2Negative electrode.With the high purity graphite is anode, TiO
2Electrode is made negative electrode, in special vacuum electrolytic furnace in the titanium metal electrolyzer in 10
-2Carry out electrolysis in the calcium chloride fused salt under the Pa, electrolysis temperature is 920 ℃, and electrolysis time is that 8h, electrolysis voltage are 3.2V.After electrolysis finishes, electrolysate is cooled to room temperature, collector electrode surface spongy material also washs with 1%HCl.Prepared electrolysate is spongy, and purity is 99.674%, reaches national titanium sponge primary standard.
Embodiment 3:
With mean particle size is 0.35 μ m, the TiO of purity＞98%
2Powder and weight ratio are TiO
2After 6% polyvinyl alcohol (PVA) of powder and 9% distilled water mix and stirs, make the electrode that diameter is 50mm, high 10mm after the mould inner pressure of Φ 50 is made type under 13MPa.After at room temperature doing 36h naturally,, make TiO at 1200 ℃ of following sintering 5h
2Negative electrode.With the high purity graphite is anode, TiO
2Electrode is made negative electrode, in special vacuum electrolytic furnace in the titanium metal electrolyzer in 10
1Carry out electrolysis in the calcium chloride fused salt under the Pa, electrolysis temperature is 950 ℃, and electrolysis time is that 7h, electrolysis voltage are 3.0V.After electrolysis finishes, electrolysate is cooled to room temperature, collector electrode surface spongy material also washs with 1%HCl.Prepared electrolysate is spongy, and purity is 99.651%, reaches national titanium sponge primary standard.
Embodiment 4:
With mean particle size is 0.35 μ m, the TiO of purity＞98%
2Powder and weight ratio are TiO
2After 6% polyvinyl alcohol (PVA) of powder and 10% distilled water mix and stirs, under 15MPa, after making type, make the electrode of 200mm * 200mm * 10mm in the mould inner pressure of 200mm * 200mm.After at room temperature doing 36h naturally,, make TiO at 1200 ℃ of following sintering 5h
2Negative electrode.With the high purity graphite is anode, TiO
2Electrode is made negative electrode, in special vacuum electrolytic furnace in the titanium metal electrolyzer in 10
1Carry out electrolysis in the calcium chloride fused salt under the Pa, electrolysis temperature is 950 ℃, and electrolysis time is that 7h, electrolysis voltage are 3.0V.After electrolysis finishes, electrolysate is cooled to room temperature, collector electrode surface spongy material also washs with 1%HCl.Prepared electrolysate is spongy, and purity is 99.645%, reaches national titanium sponge primary standard.
Claims (3)
1, direct electrolysis TiO under a kind of vacuum condition
2The novel process of preparation titanium sponge, it is characterized in that: with mean particle size is 0.35 μ m, the TiO of purity＞98%
2Powder and weight ratio are TiO
2After 5～8% polyvinyl alcohol of powder and 8～10% distilled water mix and stir, under 5～15MPa, after making type, mould inner pressure makes electrode, described electricity level at room temperature behind seasoning 24～48h, at 800～1200 ℃ of following sintering 5～10h, makes TiO
2Negative electrode is anode, described TiO with the high purity graphite
2Negative electrode is made negative electrode, in special vacuum electrolytic furnace in the titanium metal electrolyzer in 10
-4～10
1Carry out electrolysis in the calcium chloride fused salt under the Pa, electrolysis temperature is 800～1100 ℃, electrolysis time is that 5～12h, electrolysis voltage are 2.8～3.3V, after electrolysis finishes, electrolysate is cooled to room temperature, collector electrode surface spongy material and with the 1%HCl washing, prepared electrolysate is a titanium sponge.
2, by direct electrolysis TiO under the said a kind of vacuum condition of claim 1
2The novel process of preparation titanium sponge is characterized in that described TiO
2The negative electrode diameter highly is the cylindric of 50～100mm more than or equal to Φ 50mm.
3, by direct electrolysis TiO under the said a kind of vacuum condition of claim 1
2The novel process of preparation titanium sponge is characterized in that described TiO
2Negative electrode is the length of side 100～180mm, highly is the square tabular of 5～10mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100121800A CN101086073A (en) | 2006-06-09 | 2006-06-09 | Technology for direct electrolysis for preparing TiO2 under vacuum condition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100121800A CN101086073A (en) | 2006-06-09 | 2006-06-09 | Technology for direct electrolysis for preparing TiO2 under vacuum condition |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102061489B (en) * | 2009-11-11 | 2012-06-06 | 北京科技大学 | Improved process for smelting metallic titanium by electro-deoxidation method |
| CN102534260A (en) * | 2012-01-18 | 2012-07-04 | 深圳市新星轻合金材料股份有限公司 | Process method for preparing sponge titanium with sodium fluorotitanate as raw material |
| CN102586809A (en) * | 2012-03-22 | 2012-07-18 | 北京科技大学 | Method for improving TiO2 cathode deoxidizing process by utilizing carbonaceous additive |
| CN107858708A (en) * | 2017-11-23 | 2018-03-30 | 重庆大学 | A kind of method that molten-salt electrolysis prepares titanium foam |
-
2006
- 2006-06-09 CN CNA2006100121800A patent/CN101086073A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102061489B (en) * | 2009-11-11 | 2012-06-06 | 北京科技大学 | Improved process for smelting metallic titanium by electro-deoxidation method |
| CN102534260A (en) * | 2012-01-18 | 2012-07-04 | 深圳市新星轻合金材料股份有限公司 | Process method for preparing sponge titanium with sodium fluorotitanate as raw material |
| CN102586809A (en) * | 2012-03-22 | 2012-07-18 | 北京科技大学 | Method for improving TiO2 cathode deoxidizing process by utilizing carbonaceous additive |
| CN107858708A (en) * | 2017-11-23 | 2018-03-30 | 重庆大学 | A kind of method that molten-salt electrolysis prepares titanium foam |
| CN107858708B (en) * | 2017-11-23 | 2019-07-19 | 重庆大学 | A kind of method of molten-salt electrolysis preparation titanium foam |
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Open date: 20071212 |